Cyclopolymerizable compounds for 3D printing

Abstract

In one aspect, inks for use with a three-dimensional (3D) printing system are described herein. In some embodiments, an ink described herein comprises 10-70 wt. % cyclopolymerizable monomer, based on the total weight of the ink. The cyclopolymerizable monomer comprises a first ethenyl or ethynyl moiety and a second ethenyl or ethynyl moiety. Additionally, the α-carbon of the first ethenyl or ethynyl moiety and the α-carbon of the second ethenyl or ethynyl moiety have a 1,5-, 1,6-, 1,7-, or 1,8-relationship.

That which is claimed: 
     
       1. An ink for use in a three-dimensional printing system comprising:
 10-70 wt. % cyclopolymerizable monomer, based on the total weight of the ink, 
 wherein the cyclopolymerizable monomer comprises a first ethenyl or ethynyl moiety and a second ethenyl or ethynyl moiety, and 
 
       wherein the α-carbon of the first ethenyl or ethynyl moiety and the α-carbon of the second ethenyl or ethynyl moiety have a 1,5-, 1,6-, 1,7-, or 1,8-relationship, and wherein 
       the cyclopolymerizable monomer has the structure of Formula (I): 
       
         
           
           
               
               
           
         
         wherein: 
         R 1  is a hydrocarbon group having 1-4 carbon atoms; 
         R 2  is a hydrocarbon group having 1-4 carbon atoms; 
         the total number of carbon atoms of R 1  and R 2  does not exceed 5; 
         R 3  is HC═CH 2  or C≡CH; 
         R 4  is HC═CH 2  or C≡CH; 
         R 5  is 
       
       
         
           
           
               
               
           
         
       
       or a polymerizable moiety; and
 R 6  is a substituted or unsubstituted hydrocarbon group having 1-30 carbon atoms. 
 
     
     
       2. The ink of  claim 1 , wherein the cyclopolymerizable monomer is present in the ink in an amount of 20-40 wt. %, based on the total weight of the ink. 
     
     
       3. The ink of  claim 1 , wherein the α-carbon of the first ethenyl or ethynyl moiety and the α-carbon of the second ethenyl or ethynyl moiety have a 1,5-relationship. 
     
     
       4. The ink of  claim 1 , wherein the α-carbon of the first ethenyl or ethynyl moiety and the α-carbon of the second ethenyl or ethynyl moiety have a 1,6-relationship. 
     
     
       5. The ink of  claim 1 , wherein the α-carbon of the first ethenyl or ethynyl moiety and the α-carbon of the second ethenyl or ethynyl moiety have a 1,7-relationship. 
     
     
       6. The ink of  claim 1 , wherein the α-carbon of the first ethenyl or ethynyl moiety and the α-carbon of the second ethenyl or ethynyl moiety have a 1,8-relationship. 
     
     
       7. The ink of  claim 1 , wherein R 5  is selected from 
       
         
           
           
               
               
           
         
       
     
     
       8. The ink of  claim 1  further comprising:
 10-60 wt. % oligomeric curable material; and 
 up to 80 wt. % additional monomeric curable material, based on the total weight of the ink. 
 
     
     
       9. The ink of  claim 1  further comprising at least one photo initiator. 
     
     
       10. The ink of  claim 1  further comprising at least one colorant and/or one or more additives selected from the group consisting of inhibitors and stabilizing agents. 
     
     
       11. The ink of  claim 1 , wherein the viscosity of the ink is 500 cP or less at 30° C. 
     
     
       12. A method of printing a three-dimensional article comprising:
 selectively depositing layers of an ink in a fluid state onto a substrate to form the three-dimensional article, 
 wherein the ink comprises the ink of  claim 1 . 
 
     
     
       13. The method of  claim 12  further comprising partially curing the ink prior to completion of deposition of all layers of the ink, wherein partially curing the ink primarily comprises (meth)acrylate polymerization. 
     
     
       14. The method of  claim 13  further comprising post-curing the ink following completion of deposition of all layers of the ink,
 wherein post-curing the ink primarily comprises cyclopolymerizing the cyclopolymerizable monomer.